CN1047165C - Process for reduction of waste material during manufacture of acrylonitrile - Google Patents
Process for reduction of waste material during manufacture of acrylonitrile Download PDFInfo
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- CN1047165C CN1047165C CN95108690A CN95108690A CN1047165C CN 1047165 C CN1047165 C CN 1047165C CN 95108690 A CN95108690 A CN 95108690A CN 95108690 A CN95108690 A CN 95108690A CN 1047165 C CN1047165 C CN 1047165C
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- reactor
- oxygen
- containing gas
- fluidized
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- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 58
- 238000004519 manufacturing process Methods 0.000 title abstract description 8
- 239000002699 waste material Substances 0.000 title abstract description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 132
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 66
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000001301 oxygen Substances 0.000 claims abstract description 57
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 57
- 239000007789 gas Substances 0.000 claims abstract description 41
- 239000012530 fluid Substances 0.000 claims abstract description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 37
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 239000003054 catalyst Substances 0.000 claims description 29
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000004215 Carbon black (E152) Substances 0.000 claims description 11
- 229930195733 hydrocarbon Natural products 0.000 claims description 11
- 150000002430 hydrocarbons Chemical class 0.000 claims description 11
- 238000010791 quenching Methods 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 10
- 239000001294 propane Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 abstract 1
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 37
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 30
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 28
- 230000008901 benefit Effects 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 7
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 7
- 235000011130 ammonium sulphate Nutrition 0.000 description 7
- 239000003085 diluting agent Substances 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- 101000643890 Homo sapiens Ubiquitin carboxyl-terminal hydrolase 5 Proteins 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 102100021017 Ubiquitin carboxyl-terminal hydrolase 5 Human genes 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
- C07C253/26—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons containing carbon-to-carbon multiple bonds, e.g. unsaturated aldehydes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/06—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms of an acyclic and unsaturated carbon skeleton
- C07C255/07—Mononitriles
- C07C255/08—Acrylonitrile; Methacrylonitrile
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
Abstract
A process for the reduction in the amount of waste material generated during the manufacture of acrylonitrile comprising introducing an additional amount of oxygen containing gas, preferably air, in the substantial absence of any oxygenate compounds, into the upper portion of the fluid bed reactor to react with at least some of the unreacted ammonia to reduce the amount of unreacted ammonia present in the reactor effluent.
Description
The present invention relates in the unsaturated or saturated hydrocarbon polymer, ammonia and the oxygen that are preferably propylene or propane are containing in the fluidized-bed reactor of ammoxidation catalyst directly the process of ammoxidation to prepare acrylonitrile, reduce unreacted ammonia and corresponding minimizing method in a large number by ammonium sulfate that unreacted ammonia produced and the waste material that produced.Specifically, the present invention relates in the production of vinyl cyanide, be preferably the oxygenatedchemicals of air by specific position adding, thereby reduce the ammonia amount contained in the gas phase effluent of fluidized-bed reactor of in the production of vinyl cyanide, leaving in a large number at fluidized-bed reactor.Present method is carried out under the situation that does not have any other oxygen-bearing hydrocarbon such as methyl alcohol.In the actual procedure of acrylonitrile process, the generation of so a large amount of minimizing ammonium sulfate brings significant environmental advantage and economic advantages.
There are several parts of patents to relate to methyl alcohol is injected fluidized-bed reactor to produce the process of prussic acid.In addition, these reference have also been described in the production of vinyl cyanide, and methyl alcohol is injected the process that acrylonitrile fluid bed reactor is produced prussic acid.For example, USP3,911,089 and 4,485,079 all mentions methyl alcohol is injected the fluidized-bed reactor contain the ammoxidation catalyst that is suitable for producing vinyl cyanide, produces the method for prussic acid by the ammonia oxidation of methyl alcohol.In addition, Japanese patent application 74-87474,79-08655 and 78-35232 relate to the method that similarly increases or make prussic acid in the acrylonitrile process process.Second effect that Japanese patent application 74-87874 also mentions this method is to have reduced to be used for the neutral sulfuric acid amount.All these patents all relate generally to produces more prussic acid.At last, all transfer the USP5 of patent assignee, 288,473 and the patent application US Serial No.08/187 that submits to common 26 days unsettled January in 1994, the US Serial No.08/104 that submitted on August 11st, 425 and 1993,752 all relate to and use oxygenatedchemicals such as methyl alcohol to reduce the unreacted ammonia amount of leaving fluidized-bed reactor significantly.And people such as Sun propose in Chinese patent CN 1032747 the multistage reactor of sending into of air to improve the method for vinyl cyanide transformation efficiency.
Thereby the present invention relates to be preferably a large amount of unreacted ammonia amounts of leaving fluidized-bed reactor that reduce of oxygen-containing gas injection fluidized-bed reactor of air, and do not reduce the concrete grammar of the yield of vinyl cyanide simultaneously at the production period of vinyl cyanide.Present method is carried out under the situation that does not have any oxygen-bearing hydrocarbon such as methyl alcohol.
First purpose of the present invention is a large amount of amounts that reduce the ammonium sulfate that is produced during acrylonitrile process.
Another object of the present invention is to reduce the amount of the unreacted ammonia in the effluent that leaves reactor during acrylonitrile process in a large number.
Of the present invention other purpose, advantage and novelty in the following description part propose, and other parts are obvious for the those skilled in the art of having read following description, perhaps can understand by practice of the present invention.Objects and advantages of the present invention can with the concrete method that proposes in the appended claims and in conjunction with and realize or reach.
In order to achieve the above object according to the intention that embodies at this paper and describe, method of the present invention comprises with ammonia, oxygen-containing gas and is selected from propylene and the bottom of the hydrocarbon polymer of propane introducing fluidized-bed reactor that reaction generates vinyl cyanide in the presence of fluid catalyst; To not contain the oxygen-containing gas of additional amount of any oxygenatedchemicals substantially by more like this, the oxygen of promptly adding does not influence the reaction that generates vinyl cyanide substantially, but be incorporated into the top of fluidized-bed reactor with the point that is present in the reaction of at least some unreacted ammonia in the reactor and propylene, be present in the amount of the free ammonia in the reactor effluent that leaves described reactor with minimizing; The reactor effluent that will contain vinyl cyanide is sent into quench tower, and water cooling reactor effluent removes unwanted impurity and from the quench tower recover acrylonitrile.Obtaining two other advantages from enforcement of the present invention is that (1) does not produce unwanted by product in more propenal and the acrylonitrile process, the by product that (2) in most cases produce more prussic acid and need.
In the preferred embodiment of the inventive method, oxygen-containing gas is an air.
In the preferred embodiment of the inventive method, with the oxygen-containing gas added the position injecting reactor more than at least 50% at the calculated value of expansible fluidized catalyst bed height, be preferably the position more than at least 70% of the calculated value of expansible bed height, the more preferably position more than 85%, the preferred especially position more than 90%.
In another preferred embodiment of the present invention, the oxygen-containing gas of adding is introduced reactor in the position more than 100% of the calculated value of expansible bed height.
As embodying at this paper and broadly described, in another aspect of this invention, method of the present invention comprises ammonia, oxygen-containing gas and the hydrocarbon polymer that is selected from propylene and propane are incorporated into the bottom of the fluidized-bed reactor that contains the fluidized-bed ammoxidation catalyst, reaction generates vinyl cyanide in the presence of described catalyzer, wherein improve and be included under the situation that does not have any oxygenatedchemicals, oxygen-containing gas with additional amount, be preferably air by more like this, be that oxygen does not influence hydrocarbon polymer substantially, ammonia and oxygen-containing gas generate the reaction of vinyl cyanide, but be incorporated into the top of fluidized-bed reactor with the point that is present at least some the unreacted ammonia reacts in the reactor, leave the ammonia amount of reactor with minimizing.
In a preferred embodiment of the invention, with the oxygen-containing gas added top by the position injecting reactor more than at least 70% of the calculated value of expansible fluidized catalyst bed height.
In another preferred embodiment of the present invention, the oxygen-containing gas of adding is injected the top of fluidized-bed reactor by the position more than at least 80% of the calculated value of expansible fluidized catalyst bed height.
In another preferred embodiment of the present invention, the oxygen-containing gas of adding is injected the top of fluidized-bed reactor by the position more than at least 90% of the calculated value of expansible fluidized catalyst bed height.
In another preferred embodiment of the present invention, the amount of injecting the oxygen-containing gas of adding of fluidized-bed reactor is enough to and 15% at least, and preferably at least 25%, preferred at least 40% the unreacted ammonia react that is present in fluidized-bed reactor top especially.
Term " oxygenatedchemicals " according to the intent of the present invention definition comprises carboxylic-acid, ketone, alcohols, ester class or their mixture.The invention is characterized in and in the implementation process of the inventive method, do not have the above-mentioned substance of significant quantity.
The meaning of the inventive method is that it provides ammonia in a kind of simple and economic a large amount of minimizing fluidized-bed reactors to see through the method for (being unreacted ammonia), and following advantage: (1) reduces the by product ammonium sulfate during the acrylonitrile process, (2) do not use expensive oxygenatedchemicals and realize reducing that ammonia sees through and (3) have reduced ammonia and see through and do not produce more unwanted by product.In the enforcement of vinyl cyanide process,, will cause the remarkable economical advantage like this if can not implement deep well injection (deep-well injection).At present, the waste streams of discharging from quench tower contains the ammonium sulfate of suitable high density, and this makes that handling these logistics is difficult to accept on economy and environment.Reduce this ammonium salt in this logistics as far as possible and can make these logistics be accepted (as burning) by the waste treatment process that does not need exacting terms and expensive construction material, if or deeply and pour into when infeasible, can cause remarkable economical and environmental advantages.
To be described in detail the preferred embodiments of the invention now.
The present invention is by preferably in the presence of no any oxygenatedchemicals, reactor, do not influence in the position of acrylonitrile process efficient basically from allowing at least a portion excess of ammonia the preferred oxygen-containing gas that is substantially free of any oxygenatedchemicals of additional amount for air with the oxygen reaction of adding, in fluidized-bed reactor, reduce the production of the ammonium sulfate that during acrylonitrile process, produces.Be appreciated that importantly top that oxygen-containing gas is injected into reactor is actually the oxygen injecting reactor of the additional amount that will be higher than the oxygen amount that joins reactor bottom under the normal operating condition of producing vinyl cyanide.If i.e. normal operating condition requirement is 9.5: 1 at the bottom air of reactor and the ratio of propylene, then still keep this ratio, the oxygen of adding is then at the top injecting reactor.Ammonium sulfate in the waste streams that minimizing is discharged from the quench tower of acrylonitrile plant can significantly improve environmental influence and the economic situation in the enforcement of vinyl cyanide process.
In a preferred embodiment of the invention, the catalyst zone on the top of reactor (at least expansible bed height 50%) or above position (being the height more than 100% of expansible catalyst bed layer height), by a sparger air is injected fluidized-bed reactor, the position of sparger make air have an opportunity with a large amount of excess of ammonias reactions but with the ammoxidation of propylene main reaction competition that occurs in the catalyst bed bottom.According to the intent of the present invention, term " fluidized-bed reactor " not only comprises traditional fluidized-bed reactor, also comprise any reactor that can make catalyzer keep fluidized state, as circulating fluid bed reactor, transfer line reactor (transport line reactor), riser reactor or recirculation reactor.The oxygen of adding is preferably with downward angle injecting reactor, but also can be with any direction injecting reactor.Air-distributor can be made (as steel or steel alloy) with common material, wherein be provided with many nozzles, can make the gas thorough mixing but does not influence flow distribution in the reactor.
In another embodiment preferred of the present invention, the introducing position of the oxygen-containing gas of adding is in 70% level of expansible beds height calculations, preferably in the position of the 80%-90% of expansible catalyst bed layer height, most preferably in 90% above position of expansible catalyst bed layer height.The term of Shi Yonging " expansible catalyst bed layer height " is meant the catalyst bed layer height when catalyzer is in fluidized state in this manual.Promptly be present in the fluidized-bed reactor and bed height during with catalyst mix when gaseous component.
In order to obtain the highest acrylonitrile yield and/or from economic benefit, for each propylene ammoxidation catalyst, its charge proportion or operational condition are all different.The amount of leaving the excess ammonia of ammoxidation of propylene reactor also changes to some extent along with the difference of used catalyzer.The amount of the oxygen-containing gas of adding that will add is also according to the character of the type of catalyzer and reactor and change.Therefore, in practice of the present invention, the amount of adding oxygen-containing gas of injecting reactor will depend on used catalyzer and condition.In enforcement of the present invention,, generally also can use any ammoxidation catalyst although preferably use at the catalyzer of traditional oxygen/propylene than (for example more than 9.3: 1) following operation.For example, such as USP3,642,930,4,485,079,3,911,089,4,873,215,4,877,764, the catalyzer described in Japanese patent application 74-87474, the 78-35232 all is applicable to enforcement of the present invention, and all is incorporated herein by reference.
As mentioned above, for each propylene ammoxidation catalyst, its charge proportion or operational condition are all different.Between the effective date of the inventive method, the standard operation condition of existing propylene catalyzer operation can change, but also can change according to charging and catalyzer condition.As USP3,911,089 and 4,873, the operational condition and the charge ratio of the traditional mode of production vinyl cyanide described in 215 all are suitable for, and at this as a reference.
Enumerate following embodiment to describe method of the present invention just to the purpose of setting forth.
Embodiment 1
With about 12.5 tons catalyst of ammoxidation for propylene fluidized-bed acrylonitrile reactor of packing into.After several days on-line operation, with mol ratio be air/ammonia/propylene feed of 9.3/1.21/1.0 by beds, reactor batch temperature is 813 °F, roof pressure is a 12psig (gauge pressure, pound/square inch), the little hourly space velocity of weight is 0.085 hour for (WWH)
-1After adjusting charge ratio and temperature of reactor 24 hours, baseline reclaims operation (baselinerecovery run) (seeing the following form 1) and shows, propylene conversion is 98.1%, and (PPC) is as follows for per pass conversion: be converted into vinyl cyanide 80.49%, be converted into prussic acid 4.98%, be converted into propenal 0.7%, be converted into vinylformic acid 1.3%.Significantly, feed ammonia 8% by having been burnt, have the ammonia of 0.22g/scf to see through, and in the quench operation in downstream, use in the sulfuric acid of 0.22gpm and excess of ammonia.
Embodiment 2
With the condition identical with embodiment 1, and do not inject methyl alcohol (oxygen containing) steam, inject air by air-distributor in the position that is being equivalent to catalyzer expanding bed height 90%, diluent air (dilute air) is 0.52 with the mol ratio of propylene.Reclaim operation (seeing the following form 1) result and show C
3 =Total conversion rate is 99.1%, and per pass conversion is as follows: be converted into vinyl cyanide 80.5%, be converted into prussic acid 5.43%, be converted into propenal 0.6%, be converted into vinylformic acid 1.3%.Significantly, feed ammonia 7% by having been burnt, used sulfuric acid is reduced to 0.16gpm from 0.22gpm, has reduced by 27% ammonia in other words and has seen through.
Table 1
DPAR
*NH
3The total C of HCN
3 =Total embodiment air/C
3 =H
2SO
4% B.T. vinyl cyanide (C
3=) propenal
Mol ratio (gpm) ABR (g/scf) %PPC %PPC %PPC % air/C
3 =Than 10 0.22 0 0.22 80.49 4.98 0.73 98.1 9.2862 0.52 0.16 27 0.16 80.54 5.43 0.6 99.1 9.959* dilute phase AIR Proportional
Embodiment 3
With the condition identical with embodiment 2, and do not inject methyl alcohol (oxygen containing) steam, by independent air-distributor, inject air in the position that is being equivalent to catalyzer expanding bed height 90%, the mol ratio of diluent air and propylene (DPAR) is 0.51.Bottom air/C
3 =Mol ratio be reduced to 9.1 from 9.3, see and whether can reduce total air/C
3 =Than and do not influence the yield of AN or HCN, and reduce sulfuric acid consumption.Reclaim operation (seeing the following form 2) result and show C
3 =Total conversion rate is 99.2%, and per pass conversion is as follows: be converted into vinyl cyanide 79.9%, be converted into prussic acid 5.6%, be converted into propenal 0.6%, be converted into vinylformic acid 1.3%.Significantly, feed ammonia 13% by having been burnt, used sulfuric acid is reduced to 0.17gpm from 0.22gpm, compares with no independent air in other words and to have reduced by 23% ammonia through (seeing the following form 2).This shows, total air/C
3 =Than being reduced to 9.48 and significantly do not reduce the yield of AN or HCN from 10, reduced the influence of higher dilute phase air (dilute phase air) ratio.
Table 2
DPAR NH
3The total C of HCN
3 =Total embodiment air/C
3 =H
2SO
4% B.T. vinyl cyanide (C
3=) propenal
Mol ratio (gpm) ABR (g/scf) %PPC %PPC %PPC % air/C
3 =Than 10 0.22 0 0.22 80.49 4.98 0.73 98.1 9.2863 0.51 0.17 23 0.17 79.93 5.45 0.56 99.2 9.483
Embodiment 4-9
Following a series of experiments are intended to illustrate that when other condition remains unchanged the efficient of adding air separately is with adding the situation that air capacity changes.Used condition is identical with embodiment 1, but the mol ratio of feeding air/ammonia/propylene is 9.4/1.22/1.0, and initial baseline and last baseline (embodiment 4 and 5 sees the following form 3) show C
3 =Transformation efficiency is 98.7%, and the propylene per pass conversion is as follows: being converted into vinyl cyanide is 80.7%, is converted into prussic acid 5.1%, is converted into propenal 0.8%, is converted into vinylformic acid 1.7%.Significantly, feed ammonia 5% by having been burnt, have the ammonia of 0.18g/scf to see through, and in the quench operation in downstream, use in the sulfuric acid of 0.17gpm and excess of ammonia.Do not inject methyl alcohol (oxygen containing) steam, inject air by independent air-distributor in the bed position that is equivalent to catalyzer expanding bed height 90%, the mol ratio of diluent air and propylene is 0.1,0.2,0.4 and 0.6.The average result of four recovery operations (embodiment 6-9 sees the following form 3) shows under the situation that increases the DPA ratio, average C
3 =Total conversion rate is 99.2%, and the propylene per pass conversion is as follows: be converted into vinyl cyanide 80.7%, be converted into prussic acid 5.4%, be converted into propenal 0.8%, be converted into vinylformic acid 1.5%.Significantly, when adding the increase of dilute phase air, 15% of feed ammonia has been burnt, and used sulfuric acid is reduced to 0.12gpm (30%ABR) from 0.17gpm (0% ammonia sees through (ABR)), to 0.10 (40%ABR).(bottom air/the C for example of other reactor conditions at all
3 =Ratio, NH
3/ C
3 =Ratio, reaction bed temperature, reactor head pressure and catalyzer model) under all constant situation, the ratio of dilute phase air and propylene and the relation between the used sulfuric acid see the following form 3.
Table 3
DPAR NH
3The total C of HCN
3 =Total embodiment air/C
3 =H
2SO
4% B.T. vinyl cyanide (C
3=) propenal
Mol ratio (gpm) ABR (g/scf) %PPC %PPC %PPC % air/C
3 =Than baseline 40 0.17 0 0.18 80.90 5.08 0.72 98.9 9.46 50 0.17 0 0.08 80.43 5.11 0.85 98.6 9.35 dilute phase air 6 0.10 0.13 24 0.09 80.77 5.20 0.83 99.1 9.47 7 0.20 0.12 29 0.12 80.88 5.39 0.62 99.2 9.73 8 0.40 0.12 29 0.12 80.60 5.56 0.78 99.2 9.86 9 0.61 0.10 41 0.08 80 62 5.37 0.79 99.2 10.08
Embodiment 10-14
Following a series of experiments are intended to illustrate in the ammonia proportional range of broad the effect of dilute phase air (air of adding in the higher position of reactor).Repeat the described experiment of embodiment 4-9, but ammonia/propylene is than being reduced to the 1.17. condition identical with embodiment 4-9, but the mol ratio of feeding air/ammonia/propylene is 9.4/1.17/1.0, and twice baseline reclaims operation (embodiment 10-11, see the following form 4) average result show C
3 =Transformation efficiency is 98.7%, and the propylene per pass conversion is: transform vinyl cyanide 80.2%, be converted into prussic acid 5.0%, be converted into propenal 1.2%.Be converted into vinylformic acid 1.8%.Significantly, the 10-13% of feed ammonia has been burnt, and has the ammonia of 0.06g/scf to see through, and uses in the sulfuric acid of 0.07gpm in the quench operation in downstream and excess of ammonia.Do not inject methyl alcohol (oxygen containing) steam, by air-distributor, in 90% the position that is equivalent to catalyzer expanding bed height air is injected separately, the mol ratio of diluent air and propylene (DPAR) is 0.1,0.2 and 0.3.Under the situation that increases the DPA ratio, the average result of three recovery operations (embodiment 12-14 sees the following form 4) shows, average C
3 =Total conversion rate is 99.2%, and the propylene per pass conversion is: be converted into vinyl cyanide 80.1%, be converted into prussic acid 5.1%, be converted into propenal 1.1%, be converted into vinylformic acid 1.9%.Significantly, feed ammonia 15% by having been burnt, when adding the dilute phase air and increase, and compare than the sour consumption of the baseline that is at 1.22 o'clock at ammonia/propylene, used sulfuric acid is reduced to 0.06gpm (65%ABR), to 0.05 (71%ABR) to 0.04 (76%ABR).(bottom air/the C for example of other reactor conditions at all
3 =Ratio, NH
3/ C
3 =Ratio, reaction bed temperature, reactor head pressure and catalyzer model) under all constant situation, the ratio of dilute phase air and propylene and the relation between the used sulfuric acid see the following form shown in 4.
Table 4
DPAR NH
3The total C of HCN
3 =Total embodiment air/C
3 =H
2SO
4% B.T. vinyl cyanide (C
3=) propenal
Mol ratio (gpm) ABR (g/scf) %PPC %PPC %PPC % air/C
3 =Than baseline 10 0 .07 59 .06 80.51 4.89 1.2 98.9 9.44 11 0 .07 59 .04 80.11 4.89 1.3 98.3 9.37 dilute phase air 12 .1 .06 65 .03 80.39 4.96 1.2 99.3 9.43 13 .2 .05 71 .05 80.07 5.15 1.1 99.2 9.54 14 .3 .04 76 .05 79.95 5.15 1.1 99.2 9.31
Embodiment 15-17
Following a series of experiments are intended to reduce bottom air/C
3 =Can mol ratio improves the dilute phase air ratio simultaneously, see and reduce total air/C under the situation that does not influence AN or HCN yield
3 =Ratio, and further reduce sulfuric acid consumption.With the condition identical with embodiment 4-9, the dilute phase air is at the position injecting reactor of catalyzer expanding bed height 90%, and the mol ratio of diluent air and propylene is 0.2,0.4 and 0.6.And bottom air/C
3 =Than respectively from 9.1 be reduced to 8.9, to 8.7, to 8.6.Like this, total air/C
3 =More constant than the approximate 9.3-9.4 that remains on.Under the situation that increases the DPA ratio, the average result of three recovery operations (embodiment 15-17 sees the following form 5) shows, average C
3 =Total conversion rate is 98%, and the propylene per pass conversion is: be converted into vinyl cyanide 80.4%, be converted into prussic acid 4.8%, be converted into propenal 0.9%, be converted into vinylformic acid 1.4%.Significantly, feed ammonia 15% by having been burnt, and compare than the sour consumption of the baseline that is at 1.22 o'clock at ammonia/propylene, used sulfuric acid is increased to 0.21gpm from 0.19.(bottom air/the C for example of other reactor conditions at all
3 =Ratio, NH
3/ C
3 =Ratio, reaction bed temperature, reactor head pressure and catalyzer model) under all constant situation, the ratio and the relation between the used sulfuric acid of dilute phase air and propylene are as follows.Table 5
DPAR NH
3The total C of HCN
3 =Total embodiment air/C
3 =H
2SO
4% B.T. vinyl cyanide (C
3=) propenal
Mol ratio (gpm) ABR (g/scf) %PPC %PPC %PPC % air/C
3 =Than baseline 14 .0 0.17 0 .18 80.90 5.08 0.72 98.9 9.46 dilute phase air 15 .2 0.19-10 .12 80.67 4.99 0.85 98.4 9.33 16 .4 0.20-18 .12 80.62 4.81 0.89 98 4 9.32 17 .6 0.21-23 .15 79.82 4.72 0.88 97.3 9.37
These experiments show, total air/C
3 =Than can remaining unchanged, and along with the air/C of bottom
3 =During than minimizing, total C
3 =Transformation efficiency reduces, and HCN and AN yield are had detrimentally affect.In addition, can not be with this mode by adding the sulfuric acid that the dilute phase air reduces adding.This shows, under the prerequisite that does not influence reactor product distribution and yield, can only omit the air/C that reduces the bottom slightly
3 =Ratio.
Claims (18)
1. leave the method for the unreacted ammonia amount of reactor during the minimizing acrylonitrile process, comprise ammonia, oxygen-containing gas and be selected from propylene and bottom that the hydrocarbon polymer of propane is introduced fluidized-bed reactor, reaction generates vinyl cyanide in the presence of fluid catalyst; To not contain the oxygen-containing gas of additional amount of any oxygenatedchemicals substantially by more like this, the oxygen of promptly adding does not influence the reaction that generates vinyl cyanide substantially, but be incorporated into the top of fluidized-bed reactor with the point that is present at least some the unreacted ammonia reacts in the reactor, be present in the amount of the free ammonia in the reactor effluent that leaves described reactor with minimizing; The reactor effluent that will contain vinyl cyanide is sent into quench tower, and water cooling reactor effluent removes unwanted impurity and from the quench tower recover acrylonitrile.
2. according to the process of claim 1 wherein that oxygen-containing gas is an air.
3. according to the process of claim 1 wherein that the point of the oxygen-containing gas injecting reactor that will add is at the place more than at least 50% of expansible fluidized catalyst bed height calculations.
4. according to the method for claim 3, wherein with the point of the oxygen-containing gas injecting reactor added place more than at least 70% in expansible fluidized catalyst bed height calculations.
5. according to the method for claim 4, wherein with the point of the oxygen-containing gas injecting reactor added place more than at least 90% in expansible fluidized catalyst bed height calculations.
6. according to the process of claim 1 wherein that the oxygen-containing gas amount of adding of injecting reactor is enough to and 15% unreacted ammonia react at least.
7. according to the process of claim 1 wherein that the amount of the oxygen-containing gas of adding of injecting reactor is enough to and 25% unreacted ammonia react at least.
8. according to the process of claim 1 wherein that the amount of the oxygen-containing gas of adding of injecting reactor is enough to and 40% unreacted ammonia react at least.
9. according to the process of claim 1 wherein that described hydrocarbon polymer is a propylene.
10. method of producing vinyl cyanide, comprise ammonia, oxygen-containing gas and the hydrocarbon polymer that is selected from propylene and propane are incorporated into the bottom of the fluidized-bed reactor that contains the fluidized-bed ammoxidation catalyst, reaction generates vinyl cyanide in the presence of described catalyzer, wherein improve and be included under the situation that does not have any oxygenatedchemicals, oxygen-containing gas with additional amount, be preferably air by more like this, be that oxygen does not influence hydrocarbon polymer substantially, ammonia and oxygen-containing gas generate the reaction of vinyl cyanide, but be incorporated into the top of fluidized-bed reactor with the point that is present at least some the unreacted ammonia reacts in the reactor, leave the ammonia amount of reactor with minimizing.
11. according to the method for claim 10, the oxygen-containing gas of wherein adding is by the top of the position injecting reactor more than at least 70% of expansible fluidized catalyst bed height calculations.
12. according to the method for claim 10, the oxygen-containing gas of wherein adding is injected the top of fluidized-bed reactor by the position more than at least 80% of expansible fluidized catalyst bed height calculations.
13. according to the method for claim 10, the oxygen-containing gas of wherein adding is injected the top of fluidized-bed reactor by the position more than at least 90% of expansible fluidized catalyst bed height calculations.
14. according to the method for claim 10, wherein the amount of the oxygen-containing gas of adding of injecting reactor is enough to and 15% unreacted ammonia react at least.
15. according to the method for claim 10, wherein the amount of the oxygen-containing gas of adding of injecting reactor is enough to and 25% unreacted ammonia react at least.
16. according to the method for claim 10, wherein the amount of the oxygen-containing gas of adding of injecting reactor is enough to and 40% unreacted ammonia react at least.
17. according to the method for claim 10, wherein said hydrocarbon polymer is a propylene.
18. leave the method for the unreacted ammonia amount of reactor during the minimizing acrylonitrile process, comprise with ammonia, oxygen-containing gas and be selected from propylene and bottom that the hydrocarbon polymer of propane is introduced fluidized-bed reactor that reaction generates vinyl cyanide in the presence of fluid catalyst; With the oxygen-containing gas of additional amount by more like this, the oxygen of promptly adding does not influence the reaction that generates vinyl cyanide substantially, but be incorporated into the top of fluidized-bed reactor with the point that is present at least some the unreacted ammonia reacts in the reactor, be present in the amount of the free ammonia in the reactor effluent that leaves described reactor with minimizing; The reactor effluent that will contain vinyl cyanide is sent into quench tower, and water cooling reactor effluent removes unwanted impurity and from the quench tower recover acrylonitrile.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/288,118 US5466857A (en) | 1994-08-10 | 1994-08-10 | Process for reduction of waste material during manufacture of acrylonitrile |
| US288118 | 1994-08-10 |
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| Publication Number | Publication Date |
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| CN1122798A CN1122798A (en) | 1996-05-22 |
| CN1047165C true CN1047165C (en) | 1999-12-08 |
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| US (1) | US5466857A (en) |
| EP (1) | EP0696579B1 (en) |
| JP (1) | JPH0892189A (en) |
| KR (1) | KR960007550A (en) |
| CN (1) | CN1047165C (en) |
| BG (1) | BG62926B1 (en) |
| BR (1) | BR9503515A (en) |
| DE (1) | DE69516058T2 (en) |
| ES (1) | ES2144100T3 (en) |
| RO (1) | RO113344B1 (en) |
| RU (1) | RU2154632C2 (en) |
| TR (1) | TR199500886A2 (en) |
| TW (1) | TW301646B (en) |
| ZA (1) | ZA954931B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5646305A (en) * | 1995-12-27 | 1997-07-08 | Praxair Technology, Inc. | Oxygen enrichment process for air based gas phase oxidations which use metal oxide redox catalysts |
| US5886118C1 (en) * | 1997-04-14 | 2001-02-20 | Univ Case Western Reserve | Process for polymerizing acrylonitrile |
| CN1055916C (en) * | 1997-06-06 | 2000-08-30 | 中国石油化工总公司 | fluid bed reactor for ammoxidation of hydrocarbons |
| CN1056601C (en) * | 1997-06-06 | 2000-09-20 | 中国石油化工总公司 | Process for production of acrylonitrile |
| CN1055917C (en) * | 1997-06-06 | 2000-08-30 | 中国石油化工总公司 | Acrylonitrile absorbing tower |
| US5883281A (en) * | 1997-07-25 | 1999-03-16 | Praxair Technology, Inc. | Oxygen addition to reduce inerts in an acrylonitrile reactor |
| US6197855B1 (en) | 1998-09-29 | 2001-03-06 | Solutia Inc. | Nucleation of Polyamides in the presence of hypophosphite |
| US6413485B2 (en) * | 1999-05-27 | 2002-07-02 | The Standard Oil Company | Ammoxidation of a mixture of ketones to acetonitrile and HCN |
| US6358483B1 (en) | 1999-07-13 | 2002-03-19 | The Standard Oil Company | Sparger for oxygen injection into a fluid bed reactor |
| US6262290B1 (en) | 2000-08-07 | 2001-07-17 | The Standard Oil Company | Amelioration of ammonia breakthrough in an alkane ammoxidation process |
| US6743400B2 (en) * | 2001-03-21 | 2004-06-01 | The Boc Group, Inc. | Sparger configuration for fluidized bed hydrocarbon partial oxidation reactors |
| WO2017120566A1 (en) | 2016-01-09 | 2017-07-13 | Ascend Performance Materials Operations Llc | Catalyst compositions and process for direct production of hydrogen cyanide in an acrylonitrile reactor feed stream |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4070393A (en) * | 1975-03-18 | 1978-01-24 | Sun Ventures, Inc. | Ammoxidation process |
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| US3642930A (en) | 1968-12-30 | 1972-02-15 | Standard Oil Co Ohio | Process for the manufacture of isoprene from isoamylenes and methyl butanols and catalyst therefor |
| NL143415B (en) | 1972-09-04 | 1974-10-15 | Briefhouder En Papierwarenfab | CABINET OR HOLDER WITH A RETRACTABLE DRAWER AND A ROTATABLE SHUT-OFF VALVE ALONG THE TOP END. |
| US3911089A (en) * | 1972-10-06 | 1975-10-07 | Sumitomo Chemical Co | Process for preparing hydrogen cyanide |
| JPS5335232A (en) | 1976-09-14 | 1978-04-01 | Kiyonori Kikutake | Method of building collective dwelling house |
| JPS548655A (en) | 1977-06-23 | 1979-01-23 | Mitsubishi Paper Mills Ltd | Method of curing gelatin |
| JPS5487474A (en) * | 1977-12-23 | 1979-07-11 | Nec Corp | Semiconductor device |
| US4485079A (en) * | 1981-12-18 | 1984-11-27 | The Standard Oil Company | Ammoxidation of methanol to produce hydrogen cyanide |
| US4873215A (en) * | 1986-10-15 | 1989-10-10 | The Standard Oil Company | Catalyst for ammoxidation of paraffins |
| CN1023382C (en) * | 1987-03-14 | 1994-01-05 | 中国石油化工总公司 | Fluidized-bed reactor |
| US4877764A (en) | 1987-04-20 | 1989-10-31 | The Standard Oil Company | Catalyst system for ammoxidation of paraffins |
| US5288473A (en) * | 1992-10-09 | 1994-02-22 | The Standard Oil Company | Process for elimination of waste material during manufacture of acrylonitrile |
| US10475293B2 (en) | 2017-12-11 | 2019-11-12 | Igt | Gaming system and method for redistributing funds amongst players of skill games |
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- 1994-08-10 US US08/288,118 patent/US5466857A/en not_active Expired - Fee Related
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- 1995-06-27 ES ES95304532T patent/ES2144100T3/en not_active Expired - Lifetime
- 1995-07-20 TR TR95/00886A patent/TR199500886A2/en unknown
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- 1995-07-25 KR KR1019950022142A patent/KR960007550A/en not_active Application Discontinuation
- 1995-07-31 JP JP7195492A patent/JPH0892189A/en active Pending
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4070393A (en) * | 1975-03-18 | 1978-01-24 | Sun Ventures, Inc. | Ammoxidation process |
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| DE69516058D1 (en) | 2000-05-11 |
| RU2154632C2 (en) | 2000-08-20 |
| CN1122798A (en) | 1996-05-22 |
| US5466857A (en) | 1995-11-14 |
| TW301646B (en) | 1997-04-01 |
| EP0696579A1 (en) | 1996-02-14 |
| RO113344B1 (en) | 1998-06-30 |
| JPH0892189A (en) | 1996-04-09 |
| ES2144100T3 (en) | 2000-06-01 |
| BG62926B1 (en) | 2000-11-30 |
| TR199500886A2 (en) | 1996-06-21 |
| KR960007550A (en) | 1996-03-22 |
| BG99815A (en) | 1996-04-30 |
| ZA954931B (en) | 1996-02-07 |
| DE69516058T2 (en) | 2000-08-31 |
| EP0696579B1 (en) | 2000-04-05 |
| BR9503515A (en) | 1996-06-04 |
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